@article {1559, title = {Identification of 4-Hydroxycumyl Alcohol As the Major MnO2-Mediated Bisphenol A Transformation Product and Evaluation of Its Environmental Fate.}, journal = {Environ Sci Technol}, volume = {49}, year = {2015}, month = {2015 May 19}, pages = {6214-21}, abstract = {

Bisphenol A (BPA), an environmental contaminant with weak estrogenic activity, resists microbial degradation under anoxic conditions but is susceptible to abiotic transformation by manganese dioxide (MnO2). BPA degradation followed pseudo-first-order kinetics with a rate constant of 0.96 ({\textpm}0.03) min(-1) in the presence of 2 mM MnO2 (0.017\% w/w) at pH 7.2. 4-hydroxycumyl alcohol (HCA) was the major transformation product, and, on a molar basis, up to 64\% of the initial amount of BPA was recovered as HCA. MnO2 was also reactive toward HCA, albeit at 5-fold lower rates, and CO2 evolution (i.e., mineralization) occurred. In microcosms established with freshwater sediment, HCA was rapidly biodegraded under oxic, but not anoxic conditions. With a measured octanol-water partition coefficient (Log K(ow)) of 0.76 and an aqueous solubility of 2.65 g L(-1), HCA is more mobile in saturated media than BPA (Log K(ow) = 2.76; aqueous solubility = 0.31 g L(-1)), and therefore more likely to encounter oxic zones and undergo aerobic biodegradation. These findings corroborate that BPA is not inert under anoxic conditions and suggest that MnO2-mediated coupled abiotic-biotic processes may be relevant for controlling the fate and longevity of BPA in sediments and aquifers.

}, issn = {1520-5851}, doi = {10.1021/acs.est.5b00372}, author = {Im, Jeongdae and Prevatte, Carson W and Campagna, Shawn R and L{\"o}ffler, Frank E} } @article {1558, title = {Response to Comment on "Environmental Fate of the Next Generation Refrigerant 2,3,3,3-Tetrafluoropropene (HFO-1234yf)".}, journal = {Environ Sci Technol}, volume = {49}, year = {2015}, month = {2015 Jul 7}, pages = {8265-6}, issn = {1520-5851}, doi = {10.1021/acs.est.5b01970}, author = {Im, Jeongdae and Walshe-Langford, Gillian E and Moon, Ji-Won and L{\"o}ffler, Frank E} } @article {1561, title = {4-methylphenol produced in freshwater sediment microcosms is not a bisphenol A metabolite.}, journal = {Chemosphere}, volume = {117}, year = {2014}, month = {2014 Dec}, pages = {521-6}, abstract = {

4-Methylphenol (4-MP), a putative bisphenol A (BPA) degradation intermediate, was detected at concentrations reaching 2.1 mg L(-1) in anoxic microcosms containing 10 mg L(-1) BPA and 5 g of freshwater sediment material collected from four geographically distinct locations and amended with nitrate, nitrite, ferric iron, or bicarbonate as electron acceptors. 4-MP accumulation was transient, and 4-MP degradation was observed under all redox conditions tested. 4-MP was not detected in microcosms not amended with BPA. Unexpectedly, incubations with (13)C-labeled BPA failed to produce (13)C-labeled 4-MP suggesting that 4-MP was not derived from BPA. The detection of 4-MP in live microcosms amended with lactate, but not containing BPA corroborated that BPA was not the source of 4-MP. These findings demonstrate that the transient formation of 4-MP as a possible BPA degradation intermediate must be interpreted cautiously, as microbial activity in streambed microcosms may generate 4-MP from sediment-associated organic material.

}, keywords = {Anaerobiosis, Benzhydryl Compounds, Biodegradation, Environmental, Chromatography, High Pressure Liquid, Cresols, Environmental Monitoring, Fresh Water, Gas Chromatography-Mass Spectrometry, Geologic Sediments, Phenols, Water Pollutants, Chemical}, issn = {1879-1298}, doi = {10.1016/j.chemosphere.2014.09.008}, author = {Im, Jeongdae and Prevatte, Carson W and Lee, Hong Geun and Campagna, Shawn R and L{\"o}ffler, Frank E} } @article {1560, title = {Environmental fate of the next generation refrigerant 2,3,3,3-tetrafluoropropene (HFO-1234yf).}, journal = {Environ Sci Technol}, volume = {48}, year = {2014}, month = {2014 Nov 18}, pages = {13181-7}, abstract = {

The hydrofluoroolefin 2,3,3,3-tetrafluoropropene (HFO-1234yf) has been introduced to replace 1,1,1,2-tetrafluoroethane (HFC-134a) as refrigerant in mobile, including vehicle, air conditioning systems because of its lower global warming potential. HFO-1234yf is volatile at ambient temperatures; however, high production volumes and widespread handling are expected to release this fluorocarbon into terrestrial and aquatic environments, including groundwater. Laboratory experiments explored HFO-1234yf degradation by (i) microbial processes under oxic and anoxic conditions, (ii) abiotic processes mediated by reactive mineral phases and zerovalent iron (Fe(0), ZVI), and (iii) cobalamin-catalyzed biomimetic transformation. These investigations demonstrated that HFO-1234yf was recalcitrant to microbial (co)metabolism and no transformation was observed in incubations with ZVI, makinawite (FeS), sulfate green rust (GR(SO4)), magnetite (Fe(3)O(4)), and manganese oxide (MnO2). Sequential reductive defluorination of HFO-1234yf to 3,3,3-trifluoropropene and 3,3-dichloropropene with concomitant stoichiometric release of fluoride occurred in incubations with reduced cobalamins (e.g., vitamin B12) indicating that biomolecules can transform HFO-1234yf at circumneutral pH and at ambient temperature. Taken together, these findings suggest that HFO-1234yf recalcitrance in aquifers should be expected; however, HFO-1234yf is not inert and a biomolecule may mediate reductive transformation in low redox environments, albeit at low rates.

}, issn = {1520-5851}, doi = {10.1021/es5032147}, author = {Im, Jeongdae and Walshe-Langford, Gillian E and Moon, Ji-Won and L{\"o}ffler, Frank E} } @article {1565, title = {Guided cobalamin biosynthesis supports Dehalococcoides mccartyi reductive dechlorination activity.}, journal = {Philos Trans R Soc Lond B Biol Sci}, volume = {368}, year = {2013}, month = {2013 Apr 19}, pages = {20120320}, abstract = {

Dehalococcoides mccartyi strains are corrinoid-auxotrophic Bacteria and axenic cultures that require vitamin B12 (CN-Cbl) to conserve energy via organohalide respiration. Cultures of D. mccartyi strains BAV1, GT and FL2 grown with limiting amounts of 1 {\textmu}g l(-1) CN-Cbl quickly depleted CN-Cbl, and reductive dechlorination of polychlorinated ethenes was incomplete leading to vinyl chloride (VC) accumulation. In contrast, the same cultures amended with 25 {\textmu}g l(-1) CN-Cbl exhibited up to 2.3-fold higher dechlorination rates, 2.8-9.1-fold increased growth yields, and completely consumed growth-supporting chlorinated ethenes. To explore whether known cobamide-producing microbes supply Dehalococcoides with the required corrinoid cofactor, co-culture experiments were performed with the methanogen Methanosarcina barkeri strain Fusaro and two acetogens, Sporomusa ovata and Sporomusa sp. strain KB-1, as Dehalococcoides partner populations. During growth with H2/CO2, M. barkeri axenic cultures produced 4.2 {\textpm} 0.1 {\textmu}g l(-1) extracellular cobamide (factor III), whereas the Sporomusa cultures produced phenolyl- and p-cresolyl-cobamides. Neither factor III nor the phenolic cobamides supported Dehalococcoides reductive dechlorination activity suggesting that M. barkeri and the Sporomusa sp. cannot fulfil Dehalococcoides{\textquoteright} nutritional requirements. Dehalococcoides dechlorination activity and growth occurred in M. barkeri and Sporomusa sp. co-cultures amended with 10 {\textmu}M 5{\textquoteright},6{\textquoteright}-dimethylbenzimidazole (DMB), indicating that a cobalamin is a preferred corrinoid cofactor of strains BAV1, GT and FL2 when grown with chlorinated ethenes as electron acceptors. Even though the methanogen and acetogen populations tested did not produce cobalamin, the addition of DMB enabled guided biosynthesis and generated a cobalamin that supported Dehalococcoides{\textquoteright} activity and growth. Guided cobalamin biosynthesis may offer opportunities to sustain and enhance Dehalococcoides activity in contaminated subsurface environments.

}, keywords = {Bacteriological Techniques, Benzimidazoles, Biodegradation, Environmental, Chloroflexi, Chromatography, High Pressure Liquid, Coculture Techniques, Culture Media, Dichloroethylenes, Halogenation, Oxidation-Reduction, Trichloroethylene, Vitamin B 12}, issn = {1471-2970}, doi = {10.1098/rstb.2012.0320}, author = {Yan, Jun and Im, Jeongdae and Yang, Yi and L{\"o}ffler, Frank E} } @article {1563, title = {Interference of ferric ions with ferrous iron quantification using the ferrozine assay.}, journal = {J Microbiol Methods}, volume = {95}, year = {2013}, month = {2013 Dec}, pages = {366-7}, abstract = {

The ferrozine assay is a widely used colorimetric method for determining soluble iron concentrations. We provide evidence for a heretofore unrecognized interference of ferric ions (Fe(3+)) on ferrous iron (Fe(2+)) measurements performed in the dark. Fe(3+) concentrations affected the absorbance measurements, which linearly increased with incubation time.

}, keywords = {Chemistry Techniques, Analytical, Colorimetry, Darkness, Diagnostic Errors, Ferric Compounds, Ferrous Compounds, Ferrozine, Ions, Iron, Time Factors}, issn = {1872-8359}, doi = {10.1016/j.mimet.2013.10.005}, author = {Im, Jeongdae and Lee, Jaejin and L{\"o}ffler, Frank E} } @article {475, title = {Graphite electrode as a sole electron donor for reductive dechlorination of tetrachlorethene by Geobacter lovleyi.}, journal = {Appl Environ Microbiol}, volume = {74}, year = {2008}, month = {2008 Oct}, pages = {5943-7}, abstract = {The possibility that graphite electrodes can serve as the direct electron donor for microbially catalyzed reductive dechlorination was investigated with Geobacter lovleyi. In an initial evaluation of whether G. lovleyi could interact electronically with graphite electrodes, cells were provided with acetate as the electron donor and an electrode as the sole electron acceptor. Current was produced at levels that were ca. 10-fold lower than those previously reported for Geobacter sulfurreducens under similar conditions, and G. lovleyi anode biofilms were correspondingly thinner. When an electrode poised at -300 mV (versus a standard hydrogen electrode) was provided as the electron donor, G. lovleyi effectively reduced fumarate to succinate. The stoichiometry of electrons consumed to succinate produced was 2:1, the ratio expected if the electrode served as the sole electron donor for fumarate reduction. G. lovleyi effectively reduced tetrachloroethene (PCE) to cis-dichloroethene with a poised electrode as the sole electron donor at rates comparable to those obtained when acetate serves as the electron donor. Cells were less abundant on the electrodes when the electrodes served as an electron donor than when they served as an electron acceptor. PCE was not reduced in controls without cells or when the current supply to cells was interrupted. These results demonstrate that G. lovleyi can use a poised electrode as a direct electron donor for reductive dechlorination of PCE. The ability to colocalize dechlorinating microorganisms with electrodes has several potential advantages for bioremediation of subsurface chlorinated contaminants, especially in source zones where electron donor delivery is challenging and often limits dechlorination.}, keywords = {Acetic Acid, Biofilms, Biomass, Electricity, Electrodes, Electrons, Ethylene Dichlorides, Fumarates, Geobacter, Graphite, Microscopy, Electron, Scanning, Succinic Acid, Tetrachloroethylene}, issn = {1098-5336}, doi = {10.1128/AEM.00961-08}, author = {Strycharz, Sarah M and Woodard, Trevor L and Johnson, Jessica P and Nevin, Kelly P and Sanford, Robert A and L{\"o}ffler, Frank E and Lovley, Derek R} }